Method for making matt finish coatings

ABSTRACT

Coatings having a matt finish are made by applying a powder varnish composition to a substrate and thereafter reacting the varnish at a temperature of 100° to 240° C to form the matt finish coating. The powder varnish composition is a finely divided, particulate mixture of 
     I. a 1,2-epoxy compound having a melting point greater than 40° C and containing at least one 1,2-epoxy group; and 
     Ii. a salt of a polycarboxylic acid (such as pyromellite acid) containing three or more carboxyl groups and a cyclic amidine (such as 2-phenylimidazoline).

This is a division, of application Ser. No. 470,232, filed May 15, 1974now U.S. Pat. No. 3,947,384.

BACKGROUND

This invention relates to a method for making matt finish coatings whichcan be classified on the Boller gloss scale as type 258, which 20 to50%, (i.e. from matt to half-matt/half-gloss) on the basis of powdervarnishes of 1,2-epoxy compounds and salts of polybasic carboxylic acidsand cyclic amidines and conventional additives such as leveling agents.

Powder varnishes are being used increasingly for making coatings. Powdervarnishes are finely powdered synthetic compositions containing athermosetting compound, mostly a resin, a cross-linking agent, i.e.hardener and additives such as pigments, dyes, fillers, leveling agentsand so on.

Among the thermosetting powder varnish systems, coating powders based onepoxy resins are used predominantly.

By using common hardeners like amines, acid anhydrides, borontrifluoride complexes, polyamino amides, dicyandiamide or substituteddicyandiamide, coatings with more or less high gloss finish areproduced.

For special fields of application, for example smaller surfaces, glossyor half-glossy coatings are desired. Objects of large surfaces, however,are supplied with matt or half-matt finish coatings in order to avoidundesirable or unsuitable reflections of light.

In order to obtain a matt surface finish, matting agents likeparticulate (micro) silicic acid, talcum and so on must be worked intothe composition. It is often a problem to work with materials havingdifferent densities which can lead to undesirable separation of thecoating mass, to working difficulties and/or differences in coatingquality.

SUMMARY

A method has been found for making matt finish coatings withoutadditives (for example silicic acid or talcum) by using powder coatingscomprising finely divided mixtures of

I. 1,2-epoxy compounds having at least one 1,2-epoxy group in themolecule and a lower melting point greater than 40° C;

ii. an N-containing salts of polycarboxylic acid with three or morecarboxyl groups; and

Iii. cyclic amidines having the formula appearing herein. The powdercoatings are recited at 100° to 240° C., preferably 175° to 220° C toform the matt finish coatings.

DESCRIPTION

Suitable salts of polybasic carboxylic acids with three or more carboxylgroups are, for example trimellite acid, pyromellite acid, butanetetracarbonate acid, cyclopentane-tetracarboxylic acid and the like.

Cyclic amidines have the formula ##STR1## wherein R represents hydrogenor an alkyl- or aryl radical, R' is the same as R or represents acycloalkyl, heterocycloalkyl radical

R" an alkyl- or aryl substituted alkylene or arylene radical and

X represents hydrogen or the radical ##STR2## wherein R and R' are asdefined above.

Preferred alkylene and alkyl radicals contain from 1 to 12 preferably 1to 8 carbon atoms. Preferred cycloalkyl radicals contain 4 to 12 carbonatoms, preferably 6 to 8 carbon atoms. Preferred heterocycloalkyl arethe same as cycloalkyl and additionally containing one or more --N--,--S--, and/or --O-- atoms in the ring. Preferred aryl and aryleneradicals contain 6 to 12 aromatic carbon atoms, such as phenyl andnaphthyl. Preferred substituents for alkylene and arylene radicals arealkyl with 1 to 8, preferably 1 to 4 carbon atoms and aryl with 6 to 12aromatic carbon atoms, e.g., phenyl and naphthyl.

Suitable cyclic amidines are imidazolines such as 2-methylimidazoline,2,4-dimethylimidazoline, 2-ethylimidazoline,2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline2-(o-tolyl)-imidazoline, 2-(p-tolyl)-imidazoline,tetramethylene-bis-imidazoline,1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline,1,3,3-trimethyl-4-tretramethylene-bis-imidazoline,1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline,1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline,1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline andthe like. Mixtures of the imidazoline derivatives may also be used inaccordance with the invention.

The salts are made such that one or more of the carboxyl groups of thepoly-carboxylic acids are neutralized with the single-basic ordouble-basic reacting imidazoline derivatives. It is preferred tosuspend or dissolve the polycarboxylic acid in a polar aprotic solventand then feed the imidazoline in the desired molar ratio by itself ordissolved or suspended in the same solvent under stirring attemperatures between room temperature (about 23° C) and 100° C. Thereaction speed depends on the solvent and the reaction temperature.

Preferred solvents are dimethyl formamide, dimethyl acetamide andN-methyl pyrrolidone. In these solvents the reaction is completed attemperatures between 60° and 100° C in one hour. At room temperature,the salts formed are very hard to dissolve in these solvents and thuscan be recovered by filtration in over 90% yields. To increase theyields, the mother liquor is recycled repeatedly. In addition, thesesolvents have the advantage that impure polycarboxylic acids can be usedbecause impurities (especially of colored nature) are soluble in thesesolvents and they remain in the mother liquor, thereby isolating thepure salts. The mother liquor can be purified with activated charcoal.

Further lower aliphatic ketones are also suitable as solvents. Thesesolvents have the advantage that the salts formed are very hard todissolve and thus yields are nearly quantitative. There are also somedrawbacks, however, which are as follow:

1. The reaction times to complete the salt formation are longer thanwith the preferred solvents. For example, at the boiling point, 8 hoursare needed for making the disalt of the pyromellite acid with2-phenylimidazoline in acetone and, at room temperature, 24 hours areneeded.

2. Colored impurities from the polycarboxylic acids are dissolved, butnot as well as with the preferred solvents.

3. The main drawback is that the polycarboxylic acids in ketones, showslight alkalinity as compared to the preferred weak basic solvents. Forexample, pyromellite acid reacts in acetone only double-basic; intrimellite acid only single-basic, while both acids react in dimethylformamide four-basic and double basic.

Also, lower aliphatic alcohols can be used as solvents. The advantagesand drawbacks for using alcohols are between the ketones and thepreferred solvents.

For making the salts, cyclic amidines are used in such molar ratios thatat least one mole of amidine is used for each mole polycarboxylic acidup to one mole of amidine for each mole of carboxyl group in the acid.Thus, the molar ratio of amidine to polycarboxylic acid can range from 1: 1 to 4 : 1.

By using these salts as a hardener for powder varnish systems based on1,2-epoxy compounds, coatings are obtained which are technologically aswell as optically equivalent to the films and coatings produced withconventional hardeners and matting agents. The advantages realized,however, by eliminating the use of conventional additives are easierworking masses with better homogeneity of the powder. The recovery andreuse of excess pulverous materials from the first coating with thecomposition in dry state mixed in specific weight different components,like hardeners, binders, TiO₂, leveling agents and matting agents are ofgreat importance for the homogeneity and consistency. Here theconventional resin/hardener/pigment-system without addition of mattingagents where a satisfactory and well-reproducable matting effect of thefilms occurs, shows a great advantage for the industrial practice. Thematt films of the invention show great resistance to stresses, shock,bending and scratching.

Gloss rate is defined according to the method of Gardener in theMehrwinkel-Glanzmesser. It corresponds to the appropriate testingspecifications according to ASTM, U.S. Federal and TAPPI.

According to this measuring theory, 20° for highgloss measurings and 85°for matt-gloss is used. The angles 45° , 60° and 75° for thecorresponding variations are between whereby the 60° -method is broad inits use. In 9 and 10 cases, where numerous glass values are given, thisscale is taken.

The formerly described imidazoline salts are used in amounts of 2 to 15wt.%, preferably 4 to 10 wt.%, with reference to epoxy resin.

Suitable for the preparation of the finely divided mixtures which are tobe used as powder varnishes are 1,2-epoxy compounds having at least one1,2 -epoxy group in the molecule and a lower melting point greater than40° C, that is, compounds, which correspond to this characteristic, areon the one hand, polyepoxy compounds which are solid at 40° C and below,including higher-molecular compounds (so-called solid resins), and thosewhich are solid as a result of their symmetrical structure or the sizeof the carbon systems bound to the 1,2-epoxy group, and on the otherhand those which have been prepared by the reaction of liquid 1,2-epoxycompounds having more than one epoxy group per molecule with primary orsecondary amines in such quantities that the adduct contains at least anaverage of one more 1,2-epoxy group per molecule (so-called adducthardeners).

The 1,2-epoxy compounds may be either saturated or unsaturated and theymay be aliphatic, cycloaliphatic, aromatic or heterocyclic. They mayfurthermore contain substituents which under the conditions of mixtureor reaction do not cause any undesired side-reactions. Alkyl or arylsubstituents, hydroxyl groups, either groupings and the like do notcause side-reactions.

Of the solid resins those preferred for this application are 1,2-epoxycompounds having more than one epoxy group in the molecule, whose epoxyequivalent weight is between 500 and 1000.

These are the solid, polymeric polyglycidyl polyethers of2,2-bis-(4-hydroxyphenyl-propane which are obtained, for example, by thereaction of 2,2-bis-(4-hyroxyphenyl)-propane with epichlorhydrine inmolar ratios 1 : 1.9 to 1 : 1.2 (in the presence of an alkali hydroxidein aqueous medium). Polymeric polyepoxides of this kind may also beobtained through the reaction of a polyglycidyl ether of2,2-bis-(4-hydroxyphenyl)propane with less than the equimolecular amountof bivalent phenol, preferably in the presence of a catalyst such as atertiary amine, a tertiary phosphine or a quaternary phosphonium salt.The polyepoxide may also be a solid epoxidized polyester which has beenobtained for example, through the reaction of a polyvalent alcoholand/or a polybasic carboxylic acid or its anhydride with a low-molecularpolyepoxide. Examples of such polyepoxides of low molecular weight areliquid diglycidyl ether of 2,2-bis-(4-hydroxyphenyl)propane,diglycidylphthalate, diglycidylhexahydrophthalate, diglycidylmaleate andthe 3,4-epoxycyclohexylmethylester of 3,4-epoxy-cyclohexanecarboxylicacid.

Mixtures of solid polyepoxides may also be used, such as for example amixture of a polyepoxide whose melting point is between 120° and 160° Cand a polyepoxide having a melting point between 60° and 80° C (meltingpoint set forth herein is determined by the mercury method of Durrans).Suitable mixtures contain between 30 and 50 wt.% of a solid polyglycidylether of 2,2-bis-(4-hydroxyphenyl)-propane with an epoxy equivalentweight between 1650 and 2050 and a melting point of 120° to 160° C and,between 50 and 70 wt.% of a solid polyglycidyl polyether of2,2-bis-(4-hydroxyphenyl)-propane with an epoxy equivalent weightbetween 450 and 525 and a melting point of 60° to 80° C.

If a high epoxy functionality appears desirable, a preferred polyepoxideis the polyglycidyl ether of 1,1,2,2-tetra-(hydrophenyl)-ethane.

Also epoxidized polybutadiene can be applied for this purpose.

As previously mentioned, adduct hardeners can also be used in additionto the so-called solid resins, for the practice of the method of theinvention. Such solid adduct hardeners may be prepared, for example fromliquid polyepoxides of polyunsaturated hydrocarbons such as vinylcyclohexane, dicyclopentadiene, and the like, epoxy ethers of polyvalentalcohols and phenols, and aliphatic, cycloaliphatic and aromaticdiamines. For such an adduct to be suitable, its lower melting pointmust be above 40° C.

To improve the leveling characteristics of the varnishes, so-calledleveling agents are added to them during their preparation. These agentsmay be chemical compounds or mixtures of chemical compounds of widelyvarying chemical types, such as polymeric or monomeric compounds,acetals such as polyvinylformal polyvinylacetal, diethyl-2-ethylhexanolacetal, di-n-butyl-2-ethylhexanolacetal,di-i-butyl-2-ethylhexanol-acetal, di-2-ethylhexylacetaldehyde-acetal,and the like, ethers, such as the polymeric, polyethyleneglycols andpolypropyleneglycols, copolymers of n-butylacrylate andvinylisobutylether, ketone-aldehyde condensation resins, solid siliconeresins or mixtures of zinc soaps, of fatty acids and aromatic carboxylicacids and the like. Products such as Modaflow are also offeredcommercially for this purpose. The exact chemical character of Modaflowis unknown but it can be described as a complex, polymeric, effectiveliquid. Such leveling agents may be contained in the batches in amountsof 0.2 to 5.0% of the weight of the entire powder varnish.

The other components of the powder varnish mixture, such as pigments,dyes and fillers, may be present in a wide range of proportions withrespect to the 1,2-epoxy compounds.

After the powder varnish is applied to the substrate or object to becoated, the latter is heated at temperatures of 160° to 240° C,preferably 175° and 220° C, to set them. Thereafter the coating willhave the above-described advantages.

Prior to use, the powder varnish components are intimately mixed attemperatures below the hardening temperatures, extruded and then crushedinto a particulate mass. For practical application a particle size ofless than 100 microns is preferable. The maximum particle size should bebetween 30 and 50 microns.

The application of the powder varnish to the substrates or bodies to becoated is accomplished by known method, e.g., by electrostaticpowdering, fluidized-bed sintering or electrostatic fluidized-bedsintering.

The invention will now be further described with reference to thefollowing examples which are not intended to be otherwise limiting.

GENERAL DESCRIPTION OF THE METHOD APPLIED

The 1,2-epoxy compounds with the characteristics described above, knownin practice as epoxy resins, were mixed with the imidazoline saltsserving both as accelerator and hardener, with the pigments and with theadditives such as leveling agents, in the stated ratios by weight, andthen extruded and crushed. The particle size of the powder varnishcomponents was less than 100 microns. The frequency distribution of theparticle size had its maximum in the range from 30 to 50 microns. Thefinely granular mixtures for the different technological tests were thenapplied to steel sheets (70 × 150 × 0.75 mm and 70 × 200 × 1 mm) byelectrostatic dusting and then set at the stated temperatures for thestated lengths of time. The characteristics of the varnish filmsobtained were subjected to the tests listed set out hereinafter.

EXAMPLE 1

The monosalt of trimellite acid and 2-phenylimidazoline was made into apowder varnish or sintering powder with titanium dioxide and an epoxyresin plus a small amount of leveling agent in the followingproportions:

Composition of the Powder Varnish

    ______________________________________                                        Composition of the Powder Varnish                                             Solid epoxy resin on the basis of an adduct                                   of 2,2-bis-(4-hydroxyphenyl)-propane (diane)                                  and epichlorhydrin, which had been subjected                                  to an HCl cleavage and had then been reacted                                  with the additional diane and which according                                 to the manufacture had an epoxy equivalent                                    weight ranging between 900 and 1000, which                                    corresponds to an epoxy value of 0.10 to                                      0.11 and has a melting range of 90 to 100° C                                                     54.5 wt.%                                           Monosalt of trimellite acid and 2-phenyl-                                     imidazoline               5.0 wt.%                                            TiO.sub.2 in powder form  40.0 wt.%                                           "Modaflow" leveling agent 0.5 wt.%                                            ______________________________________                                    

This formulation was applied to the test sheets and after 10 minutessetting at 200° C it was tested.

    ______________________________________                                        Coating thickness          60 - 70 microns                                    Gloss        (Gardener, 60°)                                                                      33%                                                Erichsen cupping                                                                           (DIN 53 156)   8 - 9 mm                                          Cross cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2 mm                                               Buchholz hardness                                                                          (DIN 53 153)  111                                                Ball impact test                                                                           (Gardener)    80 in lb                                           (reverse impact)                                                              ______________________________________                                    

EXAMPLE 2

The disalt of trimellite acid and 2-phenylimidazoline was formulatedwith epoxy resin of Example 1.

    ______________________________________                                        Composition of the Powder Varnish                                             Epoxy resin               55.5 wt.%                                           Disalt of trimellite acid and 2-phenyl-                                                                  4.0 wt.%                                           imidazoline                                                                   TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                         0.5 wt.%                                           ______________________________________                                    

After 10 minutes of setting the test sheets at 200° C the followingresults were obtained by testing the coating:

    ______________________________________                                        Coating thickness          60 - 70 microns                                    Gloss        (Gardener, 60°)                                                                      30%                                                Erichsen cupping                                                                           (DIN 53 156)   4 - 5 mm                                          Cross cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  4                                                  Buchholz hardness                                                                          (DIN 53 153)  100                                                Ball impact test                                                                           (Gardener)    20 - 30 in lb                                      ______________________________________                                    

EXAMPLE 3

The disalt of butane tetracarboxylic acid and 2-phenylimidazoline wasmade into a powder varnish or sintering powder with titanium dioxide andan epoxy resin plus a small amount of leveling agent in the followingproportions:

Composition of the Powder Varnish

    ______________________________________                                        Composition of the Powder Varnish                                             Solid epoxy resin on the basis of an adduct of                                2,2-bis-(4-hydroxyphenyl)-propane (diane) and                                 epichlorhydrine, which had been subjected to a                                HCl cleavage and which according to the                                       manufacture had an epoxy equivalent weight                                    ranging between 700 and 875 which corresponds                                 to an epoxy value of 0.142 to 0.114 and a                                     melting range of 85 to 100° C                                                                    54.5 wt.%                                           Disalt of butane tetracarboxylic acid                                                                   5.0 wt.%                                            and 2-phenylimidazoline                                                       TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

After 15 minutes of setting the pulverous coating of the test sheets at180° C the following results were obtained:

    ______________________________________                                        Coating thickness          65 - 80 μ                                       Gloss        (Gardener, 60°)                                                                      15%                                                Erichensen cupping                                                                         (DIN 53 156)   5 - 6 mm                                          Cross-cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)   3 - 4                                             Buchholz hardness                                                                          (DIN 53 153)  100                                                Ball impact test                                                                           (Gardener)    20 in lb                                           ______________________________________                                    

EXAMPLE 4

Monosalt of pyromellite acid and 2-phenylimidazoline was made into apowder varnish or sintering powder with titanium dioxide and the epoxyresin of Example 1 plus a small amount of leveling agent in thefollowing proportions:

    ______________________________________                                        Composition of the Powder Varnish                                             Epoxy resin               54.5 wt.%                                           Monosalt of pyromellite acid and                                                                        5.0 wt.%                                            2-phenylimidazoline                                                           TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

This formulation was applied to the test sheets and after 10 minutessetting at 200° C the following results were obtained:

    ______________________________________                                        Coating thickness          70 - 80 microns                                    Gloss        (Gardener, 60°)                                                                      5%                                                 Erichsen cupping                                                                           (DIN 53 156)  7.0 mm                                             Cross-cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2                                                  Buchholz hardness                                                                          (DIN 53 153)  144                                                Ball impact test                                                                           (Gardener)    80 in lb                                           ______________________________________                                    

EXAMPLE 5

The disalt of pyromellite acid and 2-phenylimidazoline was made into apowder varnish or sintering powder with titanium dioxide and the epoxyresin of Example 1 plus a small amount of leveling agent in thefollowing proportions:

    ______________________________________                                        Composition of the Powder Varnish                                             Epoxy resin               56.0 wt.%                                           Disalt of pyromellite acid and                                                                          3.5 wt.%                                            2-phenylimidazoline                                                           TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

After 15 minutes of setting the powder coating on the test sheets at180° C the following results were obtained:

    ______________________________________                                        Coating thickness          70 - 80 microns                                    Gloss        (Gardener, 60°)                                                                      20%                                                Erichsen cupping                                                                           (DIN 53 156)   9 - 10 mm                                         Cross-cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2                                                  Buchholz hardness                                                                          (DIN 53 153)  111                                                Ball impact test                                                                           (Gardener)    80 in lb                                           ______________________________________                                    

EXAMPLE 6

The trisalt of pyromellite acid and 2-phenylimidazoline was made into apowder varnish or sintering powder with titanium dioxide and an epoxyresin plus a small amount of leveling agent in the followingproportions:

Composition of the Powder Varnish

    ______________________________________                                        Composition of the Powder Varnish                                             4 parts of a solid epoxy resin of Example 1 and 1 part                        of a solid epoxy resin according to the production of                         Example 1, however, according to the manufacture with an                      epoxy equivalent weight ranging between 450 and 500 which                     corresponds to an epoxy value of 0.200 to 0.225 and a                         melting range of 60 to 70° C                                                                     54.5 wt.%                                           Trisalt of pyromellite acid and 2-phenyl-                                     imidazoline               5.0 wt.%                                            TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

This formulation was applied on test sheets and it was tested after 10minutes of setting at 200° C with the following results:

    ______________________________________                                        Coating thickness          60 - 65 microns                                    Gloss        (Gardener, 60°)                                                                      40%                                                Erichsen cupping                                                                           (DIN 53 156)   8 - 9 mm                                          Cross-cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2                                                  Buchholz hardness                                                                          (DIN 53 153)  111                                                Ball impact test                                                                           (Gardener)    70 - 80 in lb                                      ______________________________________                                    

EXAMPLE 7

Tetrasalt of pyromellite acid and 2-phenylimidazoline was made into apowder varnish or sintering powder with titanium dioxide and the epoxyresin of Example 1 plus a small amount of leveling agent in thefollowing proportions:

    ______________________________________                                        Composition of the Powder Varnish                                             Epoxy resin               56.5 wt.% -Tetrasalt of pyromellite acid                                      and 3.0 wt.%                                        2-phenylimidazoline                                                           TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

After 10 minutes of setting the powder coating of the test sheets at200° C the following results were obtained:

    ______________________________________                                        Coating thickness          75 - 80 microns                                    Gloss        (Gardener, 60°)                                                                      30%                                                Erichsen cupping                                                                           (DIN 53 156)   9 - 10 mm                                         Cross-cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2                                                  Buchholz hardness                                                                          (DIN 53 153)  111                                                Ball impact test                                                                           (Gardener)    70 in lb                                           ______________________________________                                    

EXAMPLE 8

The disalt of pyromellite acid and 2,4-dimethylimidazoline was made intoa powder varnish or sintering powder with titanium dioxide and the epoxyresin of Example 1 plus a small amount of leveling agent in thefollowing proportions:

    ______________________________________                                        Composition of the Powder Varnish                                             Epoxy resin               54.5 wt.%                                           Disalt of pyromellite acid and                                                                          5.0 wt.%                                            2,4-dimethylimidazoline                                                       TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

After 10 minutes of setting the powder coating of the test sheets at200° C the following results were obtained:

    ______________________________________                                        Coating thickness          70 - 80 microns                                    Gloss        (Gardener, 60°)                                                                      40%                                                Erichsen cupping                                                                           (DIN 53 156)   8 - 9 mm                                          Cross-cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2                                                  Buchholz hardness                                                                          (DIN 53 153)  166                                                Ball impact test                                                                           (Gardener)    20 - 30 in lb                                      ______________________________________                                    

EXAMPLE 9

The disalt of pyromellite acid and 2-(m-tolyl)-imidazoline was made intopowder varnish and sintering powder with titanium dioxide and the epoxyresin of Example 1 plus a small amount of leveling agent in thefollowing proportions:

    ______________________________________                                        Composition of the Powder Varnish                                             Epoxy resin               55.5 wt.%                                           Disalt of pyromellite acid and                                                                          4.0 wt.%                                            2-(m-tolyl)-imidazoline                                                       TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

After 10 minutes of setting the powder coating on the test sheets at200° C the following results were obtained:

    ______________________________________                                        Coating thickness          65 - 75 microns                                    Gloss        (Gardener, 60°)                                                                      40%                                                Erichsen cupping                                                                           (DIN 53 156)   8 - 9 mm                                          Cross cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2                                                  Buchholz hardness                                                                          (DIN 53 153)  100                                                Ball impact test                                                                           (Gardener)    60 - 70 in lb                                      ______________________________________                                    

EXAMPLE 10

The disalt of pyromellite acid and 2-benzylimidazoline was made into apowder varnish or sintering powder with titanium dioxide and the epoxyresin of Example 1 plus a small amount of leveling agent in thefollowing proportions:

    ______________________________________                                        Composition of the Powder Varnish                                             Epoxy resin               55.5 wt.%                                           Disalt of pyromellite acid and                                                                          4.0 wt.%                                            2-benzylimidazoline                                                           TiO.sub.2 in powder form  40.0 wt.%                                           Leveling agent (as in Example 1)                                                                        0.5 wt.%                                            ______________________________________                                    

This formulation was applied to the test sheets and after 10 minutessetting at 200° C it was tested with the following results:

    ______________________________________                                        Coating thickness          60 - 70 microns                                    Gloss        (Gardener, 60°)                                                                      40%                                                Erichsen cupping                                                                           (DIN 53 156)  8.0 mm                                             Cross-cut adhesion test                                                                    (DIN 53 151)  Gt 0                                               Mandrel bending test                                                                       (DIN 53 152)  2                                                  Buchholz hardness                                                                          (DIN 53 153)  111                                                Ball impact test                                                                           (Gardener)    80 in lb                                           ______________________________________                                    

What is claimed is:
 1. Method for making matt finish coatings whichcomprisesa. applying a powder varnish to a substrate, said powdervarnish comprising a finely divided mixture ofi. a 1,2-epoxy compoundhaving at least one 1,2-epoxy group in the molecule and a lower meltingpoint greater than 40° C; and ii. a salt of a polycarboxylic acid havingthree or more carboxyl groups; and a cyclic amidine having the formula##STR3## wherein R is H, alkyl or aryl;R' is the same as R and inaddition cycloalkyl, or a heterocycloalkyl radical obtained bysubstituting one or more --N--, --S--, and/or --O-- atoms in acycloalkyl ring; R" is alkyl and aryl substituted alkylene or arylene;and X hydrogen or the radical ##STR4## wherein R and R" are as definedpreviously; and b. thereafter reacting said powder varnish at atemperature of 100° to 240° C to form a matt finish coating.
 2. Methodof claim 1 wherein said salt is present in amounts of 2 to 15 weightpercent, based on the epoxy compound.
 3. Method of claim 1 wherein thepolycarboxylic acid and the cyclic amidine are in a molar ratio of 1 : 1to 1 :
 4. 4. Method of claim 1 wherein the polycarboxylic acid isselected from the group of trimellite acid, pyromellite acid, butanetetracarboxylic acid and cyclo-pentanetetracarboxylic acid.
 5. Method ofclaim 1 wherein the cyclic amidine is 2-phenylimidazoline.
 6. Method ofclaim 1 wherein the salt of pyromellite acid and 2-phenylimidazoline isused.
 7. Method of claim 1 wherein the salt is the reaction product of 1mole of pyromellite acid with 2 or 4 moles 2-phenylimidazoline used.